Interpolymers of asymmetrical dichloroethylene



agitation until polymerization has proceeded to the desired extent.

Patented July 10, 1945 o 2,330,909 H l v mnronmnsor ASYMMETBIOAL i -nrcmionon'rnnann s l 1 namlawurmi Arnold, Marshaliton, assert,

Lowrance Borough, W

ilmingtombei assignors,

to E. L du Pont de Nemours a Company,

n, Del., a eorporation of Delaware Serial No. 349,000

No Drawing, I madam-m1, 1m,

"same (01. zoo-s8)" e invention relates new, polymeric prod: note and more particularly to products obtained saturated compounds. H Asymmetrical dichloroethylene. gpolymerizes by the, copolymerizatiomof polymerizable unreadily under ordinary polymerization conditions to yield a polymer which is diflicultly fusible under molding conditions, and which is rapidly, decomposed at temperatures only slightly above its softening point, Moreover, the articles formed by molding the polymer even under carefully controlled conditions show pronounced brittleness. For these reasons the fabrication of useful articles from the polymer presents a diiilcult problem. H This invention has as an object the prepare.

tion of polymers of asymmetrical dichloro 1 ethylene which are readily molded and of greater stability at temperatures above their softening point. A further object is thepreparationof dichloroethylene polymersof reduced brittleness. Another object is thepreparation ofdesirable molding compositions. Other objects will appear hereinafter. r o

These objects are accomplished by the following invention which comprises copolymers], of 40-95% asymmetrical dichloroethylene with 560% (of the total polymerizable components) of a ketone, in which one immediately adjacent to the carbonyl group is part of a hydrocarbon, preferablyan alkyl and still more preferably ad flweri i. e., one to six, carbon alkyl, radical 'andthe other is attached by an ethylenicldouble bond to (a methylene group. .In. the preferred practice, of the invention, asymmetrical dichloroethylene is mixed with 10-50% by weightof a ketonein which one of the carbon atoms inunediatelyl adjacent to the carbonyl group is part of .ahydrocarbon radical. e. g., an alkyl, aryl, aralkyl, or cycloalkyl group, and the otheris attached by ,janethylenicdouble bond to a methylene group andby-a single bond,

to hydrogen, a lower, i. e., one to six carbon, alkyl group, an aryl group, or halogen, andthe mixture is emulsified in an acidiclaqueous medium containing 1-3% of an emulsifying or dispersing agentand 0.1-2% of a water-soluble oxygenliberating polymerization catalyst such as hydrogen peroxide. The emulsion is placed in-a pressure vessel equipped with. some means ofagitation and heated at a constant temperature of betweenAO-GOQ; with constant or intermittent of j the carbon atoms Q There are two convenient methods mining the progress offpolymerization: l

i (1) Periodicdeterminationotspeoific gravity. As polymerization proceeds, the specific gravity of, the emulsion increases; markedIyQthe: extent of the increase when polymerization is complete depending primarilyion theinitial concentration of thernonomers and the monomer ratio. It usually is necessary to, standardize the method with a given monomerY-dispersinglmediurn more ture, checking (the specific gravitvagainst the polymer cont nt as determined by analysis.j@.The

specific gravity1,may be determined conveniently by means of awestphal balance? 1 (2) ,jPerio'dic precipitation of samples. In this method, samples of the emulsion are periodically,

withdrawn, rrom,, ,;the polymerization ves el, weighed, steam distilled to remove unpolymerized monomers, and precipitated by theaddition of electrolyte such as aluminurnsulfate. The precipitated, ipolymer is repeatedly washed with water anddried rapidlyat elevated temperature. f, from the weight of theemulsion sample and theweight of the precipitated poly: mer, the extent of, polymerization can be readily calculated.

when polymerisation hasproceeded to thede sired extent, the emulsion is withdrawn and steam distilledto' remove any residual i monomer which, may" be. present. It is thendilutedcwith f equalyvolurne"otjwater and precipitated by the addition with rapidstirring ofanappropriate quantity-of an aqueous solutionfcontaining an electrolyte such as aluminum sulfate, calcium chloride, sodium chloride, sulfuric acid, jphos phoric acid, hydrochloric acid, orfthe'like. The precipitated polymer is" filtered? on, washed thoroughlyfwith water until all traces of electrolyte and dispersing'agentare removed," and dried. To facilitate 'dr'ying, the polymer-may, ifdesired, begiven a final wash-with a low-:boil ing water miscible organic liquid whichis not a solvent for the polymer. Lower aliphaticalco- 1, o hols or mixtures of these withv smallcpercentasfi so of aromatic hydrocarbons are suitable mums purposes, Thetdnai wash witnalcoholor alco l.

hol-aromatic hydrocarbon mixtures, frequently improvesthe stability or the idlymerbyl remove ing traces ,of', low molecular weight polymeric Products and impurities introduced with the t persing agent. 1

i The monomer, is preferably emulsified before polymerization in anacidic medium. is done becausethe copolymerization of: asym;

metrical. dlchloroethylene is quite slow n neutral or alkaline media. and the products obtainedare are suitable.

. "Ihe molecular less stable than those produced in acid media. It i ther f re advantageous to add to the emulabout 2.5-3.5.

' Because the copolymerizations are preferably conducted in acidic media, it is necessary to ae-x lect the emulsifying or dispersing agent .vely

carefully since certain of these materials are not suited to use in acidic media. Dispensing agents which are suitable for use in acid media include ,salts of true sulfonlc acids, such as alhl naphthalene sulfoniclacids, long chain allryl sulfonic 1 l acids, and salts of acid sulfuric-esters of ions chain alcohols, such as the sodium salt of a-acetoxyoctadecylsulfuric acid. 7 v In addition to hydrogen peroxide a number of water-miscible polymerization catalysts may be used. These include perborates, persulfates, peressential to employ only water-miscible catalysts. Catalysts which are soluble in the monomer mixture' may also be used. Among these are acetyl emulsified in a dispersing medium having the r same composition as that described in Example acetates. peracetic acid, and the like. It is not benzoyl peroxide, benzoyl peroxide, dibutyryl peroxide. lauryl peroxide, and succinyl peroxide.

Emulslflcation of the monomer mixture in the dispersin or emulsifyingagent maybe accom plished by simple Stirring or agitation as by shaking or through theuse of aso-called turbulent flow mixer. In carrying out the'emulsiflca-- tionit is necessary to avoidelevated temperatures since monomeric asymmetrical dichloroethylene boils only slightly above room temperature.

[The in which the polymerization is, carried but must be made of a material which is not attacked by acids, andwhich does not retard the polymerization. It has been found that glass, ckel', stainless steel, and enamel-lined vessels weight or 'thecopolymers' is influenced by polymerization conditions. In gen eral, high temperatures. hi h catalyst concentrations, and. low monomer concentrations lead to relatively low molecular weight products, while 'low' tem ratures, low catalyst concentrations, and high'monomer concentrations favor the production of relatively high molecular weight products.

The more detailed practice of the invention is illustrated by theffollowing examples, wherein, unless otherwise specified, parts given are by weight. There are ofcourse many forms of the invention other than these speciilc embodiments.

I Example-I v A mixture of .70 parts oiasymmetrical dichlo-' roethylene and 30 parts of methyl vinyl ketone is emulsified by vigorous shaking in a pressure vesselwith a mixture containing 150 parts by volume of water, 2 parts by volume oi. 30% hydrogen peroxide, 8 parts by weightof a 50% solution of the sodium, s lt of a-acetoxyoctadecylsulfuric acid and 0.2 part by volume of concen ti tted hydrochloricacid. The vessel is closed and-heated at 50 0. for approximately 67 hours ujritifiritermittent shaking. At the end of this time the specific gravity as determined at room temperatureis 1.125. The emulsion is filtered throu h cloth and "diluted with approximately an equal volume of water. This mixture is heated to apaluminum sulfate solution. The product is repeatedly washed four to five times with water tem r ture. After dryinaltiie polymerfamounts to.68 parts. Analysis shows that it contains 69% by weight of unsymmetrical diehloroethylene. It

is readily soluble in dioxan, giving a colorless solution from E' which clear, exceptionally tough films can bejcast. On molding under pressure, a light-colored; very tough article which becomes flexible at'about 56C. is produced.

- mass 11- A mixtureof 80 parts or asymmetrical memo-- roethylene and parts of methyl vinyl ketone is I. Theemulsion is heated in a pressure-tight glass vessel at 60C. for 46 hourswith occasional agitation. lit the end of this time the specific gravity at room temperature is 1.160. The mixture is steam distilled, diluted with an approximately equal volume of water, and precipitated by the addition of 10% aluminum sulfate solution, 92 parts of product beingobtained. Analysis shows that it contains 63.8% by weight of polymerized. asymmetrical dichloroethylene. It can be molded to a tough article which becomes pli-. able at approximately 36 C. when heated in an oil bath. This can be dissolved readily in dioxan to give a 15% solution whose viscosity at C. is 16.5 centlpoises. i 7 Example III A mixture of 275 parts. of asymmetrical ditrated hydrochloric acid, 4.2 parts by volume of-'- hydrogen peroxide, and 25 parts by weight of an approximately 50% solution 01' thesodium salt of a-acetoxyoctadecylsulfuric acid in water. The mixture is heated'at C. with occasional agitation for a total of 138 hours. At the end of this time it is steam distilled to remove residual monomer, filtered through cloth, anddiluted with approximately an equal volume of water. Five parts of'epichlorohydrin is then stirred in, and the mixture cooled to approximately C. The polymer is precipitated in the form of small granules by the addition of a small volume of 10% aluminum sulfate solution. These are washed several times with water, once with 0.5% sodium hydroxide solution, and again several times'with water. 'A total 0153505 parts of product is obtained. Analysissh'ows that it contains 51.9% by weight of asymmetrical dichloroethylene. It dissolves readily in dioxan to give a 15%solution whose viscosity at 25 C. is 176 centlpoises and can be molded at approximately 160 C. under pressure of about 8000 lbs/sq. in. to very tough articles which become pliable at approximately 86 C. when heated in an oil bath.

, y EflmpleIV Amixture of 32.5 parts of asymmetrical dichloroethylene and 17.5 parts of methyl vinyl ketone is emulsified in a mixture consisting of parts by volume of water, 0.1 part by volume of 12 and finally with methanol, and then dried at room .mately. 48 C.

r can readily be molded at; 160C.

mixture is placed in a glass pressure vessel and heated at 40-"-45 c. for 138 hours with occasional imitation. The polymer is precipitated and washedlas in ExampleI, and dried at room temperature. The yield amounts to 43.5 parts. it

Analysis of the productshows that itlcontains chloroethylene. It molds at,115fl20. C. to a. tough article which becomes pliable atlapproximately 57 C wh'en heated in an oil bath; ,Itldissolves readily in. dioxanTto give a clear1solution from Sheets ofth'e copolymer, iormedby hot pressing.

on being subjected. to. a cold" rolling pemacm,

V A mixture or 51511951138 of smash a1 chloroethylene, 27.5 parts of methyl vinyl ketone and 2 partsoi'. ethylenefoxide is emulsified ina pressure vesseldn a dispersing agent/catalyst mixture having the same composition asthat in the preceding example. The rmixtureis heated at 45-50" C. with oceasionalvigorous agitation for a total of 93.5 h'ours. Atlthe end of this time it is steamdistilled to remove residual monomer,

diluted with an approximately equal volumeof. water, and precipitated by the additionof aluminum sulfate solution; The polymer is re- 3'. peatedly washed i'ourto five timeswith distilled waterand then stirred for about mlnutes with a 1% solution of potassium hydroxide initially. heated to60 C. It is flltered washed with water until alkali free,- and finally washed with warm methanol. It is then mixed with an ether solution containing 0.5 part of phenoxypropylene oxide and l a current of airis passed over the suriaceoi th'e 1 mixturewhile. it] is being stirred until the ether has completely evaporated. A total 0142 parts of d d product is obtained- Analysisshows it con- ,tains 44% by weightofpolymerizedasymmetrical dichloroethylene. :It dissolves readily in dioxan to give a clear solution whose viscosity is 180 centipoises. Films flowed from thissolution are colorlesstough, and'elastic. The copolymer can-be :molded readily to alight-colored, clear, tough it article" which becomes pliable at approxi- .A mixture of 10; part s of asymmetrical Qdichloroetiiylene and 10 parts or phenylvinylketone of the sodium salt of acetoxyoctadecyl sulfate in water. The mixture is heated at 45 C.with occasional agitation for atotalof 48 hours. Atthe endot this time the j polymer is precipitated, washed, and dried as in the preceding example.

A total 01-0 parts oiproduct is This ummy- Ninety-four and a halt parts of an aqueous solution containing approximatelyfizper cent by weightloi' the sodium salt ofthe sulfonic acid derivedfrom the petroleum oil lmown as White Oil, and 3.75 parts oi ammonium persuli'ate are dissolved in 1400 parts of wateni flhepH oithis solution is adjusted. to 2.45 by the appropriate addition of formic acid solution oi 89 percent show a tensile strengthfoi r 10.000- 13,500. lbs./sq.

. of a-acetoxyoctadecylsuliuric acid inwater. The

concentration. tafmntm r oo mortmsff 1 solution with;30 parts or; n ymmetrical mummethylene and 20 mmorm tnn 99ml tone is placed in a glass p es ure vessel and- 9 vessel flushed out lwith oxygen-free nitrogenbe fore closing. The emulsified by vigor 0 1 a i ati n amb s d fl w flnti wiv 1 ytureoilofp. fora'period oi '72 h'ours, 4ttheend thisttime the vessel is openedand theemulsion removed and diluted with anapproldma l qlllll ,volumeor water. 'Iheresultingmixtureis heated n npro im w mw c. and y the interpolymer precipitated bythe addition of approximately 15 I of 10 per" cent aluminumr sulfate, solution.

The was 1 washed four times with warm wa to removeoccluded dispersing iagent, n

thenfdried, porti not the product was pressed it I .out between heated platesat 130 2C.,uaing arreslsureof approximately2000lbs./sq.in, Th r sult. l m "sheet s owecrexceu t strength. gy,

.nessm...

A mixture:'oi'g40}1.-parts of unsymmetricalwdichloroethylene'and mparts of methyl isopropenyl ketone" is polymerized and the polymerisolated as in Example: VII. The yield oi' polymerlamounts to parts; :JOnpressing out between hot plates at 130 cflusingia pressure ofapproximately 2000 lbs./sq .in.,thepolymertproducesatough,-flexible sheet whichcan befolded over repeatedly without I breaking The sheet is somewhat less rigid than that otlExampleVII. 1. l In applying the invention, asymmetricaldi chloroethylene may be copolymerized with""any polymerizable ketone in which one of thecarbon atoms immediately adjacent to the. carbonyl groupisapart of a-hydrocarbon -radical,e. gr sp: .alkylmaryl, :aralkyl, or cyeloalkyl zrouprj'and the other is attached byflan ethylenic double bondto V a=methylene group to yield copolymers; containing .40.-95%.=o1' theyasymmetrical dichloroethylene in combinationlwith theiketone. 'I'herketone is thusone wherein one valence of the carbonyl group is attached. to acalrborrinv turn attached to a methylene (CH1) group; the remaining valence of the carbonylgroupbeing satlsfled by a hydrocarbon radical The .polymerizable ketone is repl' il ntedby the iormula uhereili a a ysmal-b ll radical and is; is d semh losem, a kyl preferably of one to 1;;

carbon atoms oraryla, l I 1 The copolymers containingl5-60% oi the ketone are tougher than copolymers of greater or}: less ketone content, are moreystable and can be mold.-

ed at highertemperatures than copolymerswof less ketone content, .havebetter molding. characteristics, less tendency to be rubbery; andare more uniform. -;They.do not haveythe watehsen sltivity of the copolymersof higherketoneicon tent. Furthermore, they can beoriented by rolli ing whereby improvedstrenaths maybe obtained; lWith less than 5%;ketonerthe ,product has the disadvantageous characteristics lot unmodified dichloroethylene polymer, namely, a softening a temperature so nearthedecomposition temperature that thereis difllculty inmaking shaped objects underthe influence of heat and pressure; and is lacking in tensilestrength and toughness". 3

A copolymer tormed froma reaction mixture contain ng more than unsaturated ketone j possessesundesi a'ble water sensitivity and also .7! shows deficiencies intensile strength. Thus when tone would be excluded.

' advantage from the practical standpoint.

products containing more than 95% unsymmetsoftening and become tacky at relatively low temperature. Their strength is poor and they show'yery sIOwretraCtiOn'When stretched. Cold the effector changing each of (actors, and ordinarily considerable experimentation is required before conditions are found by whichfa given monomer mixture can be made. to

drawing or cold rolling 'doesnot materialiy-improvel;thelr strength. i In general, their physical *properties ;,are such as to preclude extensive application in varlous'plastics and coating applicatlons. Furthermore, these polymersare sensitive to water (whiten on exposure to water) and are attacked by alkalies. When the ketone is methyl isoprope'nylketone or phenyl vinyl ketone,'-the co'pol'ymers containing more than 60% 'ketone,

although considerably higher softening than similar compositions'containing methyl vinyl lietone tendto be brittle. They are not materially improved bycold drawing for cold rolling. As with the methyl vinyl ketone polymers they are excessively sensitive'to water and alkalies.

, The 40 to 95% dichloroethylene copolymers when molded or formed by heat and pressure show-excellent strength and toughness. In the iorm'of :sheets or films they can be repeatedly bent around a small radius without "breaking and they show good resilience. Their strength and toughnessare improved markedly'by cold drawing'or cold rolling... Cold rolled-or cold drawn sheets 'or foils may show tensilestrengths in excess of 15,000 lbs. per sq. in. .The 40 to 95% copolymers are also much less sensitive to water tents... v H

The 40 to 95% dichloroethylene copoiymers are more resistant to burning than those containing morethan 60% ketone. I

The copolymers containing more than 60% ketone are, for the majority of plastics uses, "too susceptible to the action of a=wide variety oforganic solvents The 40 to95% dichloroethyl- (are products while readily solublein selected solvents are more resistant to thegeneral run of solvents and cantherefore be used in applications 60% ker from which those containing morethan The copolymers containing more than 95% unsymmetrical dichloroethylene soitenonly slightly below their decomposition point. They are therefore subject to considerable decomposition and P degradation when molded. Furthermore very high molding temperatures are required, adis- The rical dichloroethylene show poor strength as compared with the 40 to 95% products. The solubility of the 40 to-95% dichloroethylene products is better than that of those containing-more than 95% unsymmetrical dichloroethylene.

The stability to heat and light of products con- Generally speaking, in the preparation of the 40 to 95% copolymers there is more or less variai'.ion;hetween the original composition of monomer-mixture and that of the final product. The

I extent of this-variation appears to depend both on the polymerization conditions and on the stirring rapidly.

. polymer having thefidentical composition. U y H Asymmetrical dichloroethylene is readily pre-' paredirom p'-trichloroethane by reaction with alcoholic" potassium hydroxide according to the method described by Regnault, J. prakt'. Chem.

1;,(1), 8, (1839), or by treatment with aqueous caustic sodasolution. Methods describedinGerman Patent"52 9 ,604 (I. G.) andBrltish Patent '436,133,'ma y-also beam lied. According tothe preferred method, beta-trichloroethane is" slowly dropped into an aqueous solutionoi sodium hymonomer so formed may beused directly with good results for copolymerization, or, if desired,

and alkalies than those with high ketone concan be subjected to further purification by distil lation. Depending upon theconditions under whi'chthe reaction is carried-out. the monomer may boil in the range-oi approximately 31' C,-3'7

C. One fractionation througha good column generally yields monomer boiling over a narrow-range within the limlts'oi 31-33! C. Or the unsaturated ketones which it is preferred to use in: the preparation or the copolymers of this invention, methyl vinyl ketone is most conveniently prepared by the hydration of monohydration of the primary reaction productaaccording to the method described by Pepper, BritishPlastlcslO, 609 (1939). Phenyl-vinyl'ketone isproducedby the reactionoi' aoetophenone with formaldehyde in the presence or ammonium chloride, according to the'method "described by Van Merle and Tollens, Ber.36, 1355 (1913). Alphachlorovinyl ketones may be prepared by.1the chlorination of alkyl vinyl ketones followed by dehydrohalogenation otthe product, as described in us. Patent 2,173,066; "rile reaction ot acid halides with ethylene hydrocarbons in the presence of Friedel-Craits type catalysts may in cer-. tain instances be used in the preparation oi polymerizable unsaturated ketones. Other alpha methylene ketones which may be employed to give the copolymers of thisinvention include ethyl. propyl, isopropyl, butyl, hexyl and octyl vinyl ketone, phenyl vinyl ketone, p-tolyl vinyl ketone, benzyl vinyl ketone, cyclohexyl vinyl ketone, 2- chloro-l-buten-3-one, 2,-methyl-1-buten-3-one, 2-phenyl-l-buten-3-one. etc. Alkyl vinyl ketones andespecially lower-alkyl vinyl ketones are Prein'gpointoithe copolymer. V V In the preferred practice oi.'-- the inventionthe i'erred for reasons of cost and the higher sottencopolymers are produced by the emulsion Process This process, as illustrated by theforegoing examples, may, if desired; be modified in several ways. For example, only one component may be emulsified in the catalyst-dispersing agent soluoriginal monomer, proportions. "Factors inthe polymerization process which afiect these varia-' tions are. method, catalyst andcatalyst concentration, dispersing agent (it emulsion method is used) and concentration thereof, temperature, and voiwgen concentration in the polymerization vessel. It is not possible to predict in advance tion', andpolymerization of this materialcinitiated, the second. component being added continuously or portion-wise over. the period of time required for complete polymerization ol'the' first component. Theemulsion processmay also be so conducted that the mixture of monomers and the emulsifying catalyst medium are continuously clined heated tube, and a the mixture forced a,sao,ooc introduced into the lower end ot a slightly intween 0.14%, wider limits may be used, for example, irom about 0.01-3%. desired-polymerr sn the tube at'such a rate thatat the tempemme b81118 r lymerization istvirtuallyg-ry completeawhennthe mixtureflreaches .the upper end of the tube. ,0 In'a'iurther modificationof the emulsion process the mixture of monomers may be polymerized: in an indifierent organic solvent which is a solvent for the monomers but a nonsolvent. for the copolymers, and which contains a small percentage of an emulsifying agent which is soluble in the solvent and shows somewsolvent action on the monomers, or polymer. 1 a

Other methods of polymerization may, course, be employed. For example, the comlarteniperature' being used. "It is frequently desirable to'sweep out the vessels withinert gases such as nitrogen or carboncdioxidebefore initiat ing polymerizatiom This'procedure serves to remove. any oxygen remaining iii-the vessel and H frequently results in more rapid polymerizationfi y Compressedinertgases may, ii desiredfbe introduced into the polymerization! vessel to give ponents may be copolymerizedxin bulk without clear, vitreous mass having the shape of the container, and it may, if desired, be dissolved in appropriate solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, .ketones. esters, or dioxan and precipitated in finely divided form by the addition of appropriate nonsolvents such as water, lower aliphatic alcohols, or aliphatic hydrocarbons. i i i There are two. modifications of the solution method which may be applied: (a) polymerization in a medium which is a solvent for the monomer mixture but a nonsolvent for the polymer, and (b) polymerization in a medium which is a solvent both for the monomer and the polymer. In the first modification solvents such as aliphatic alcohols, aliphatic hydrocarbons, and mixtures of water and lower aliphatic alcohols may be used, and the copolymers are usually preadded diluent, in a vessel having any desired iorm. The product by this method is usually. a

cipitated as they are formed, in finely divided or fiocculent form. In the second modification of the solution method the products are obtained in the form of more or less viscoussolutions which may, if desired,be applied directly as coating compositions. l The granular" method may also be employed.

This involves rapidly agitating the monomer mixture containing a small percentage of the peroxidic polymerization catalyst with an aqueous solution containing a small percentage (up to about 3%) of a protective colloid of the type of soluble starch, methylated starch, partially hydrolyzed polyvinyl acetate, the sodium salts of polymers or interpolymers containing acrylic or methacrylic acid, polymethacrylamide, sodium starchglycolate, sodium celluloseglycolate, etc., in a vessel equipped with a reflux condenser and at such temperatures that moderate reflux is maintained. Or the polymerization may be conducted in a closed vessel at higher temperatures provided tion is suspended. The granules are readily filtered from the mixture, washed free of occluded protectivecolloid, and dried.

Although the preferred temperature range at which polymerization is carried outis 40-60" C.,

wider ranges of temperature may be employed;

, merization proceeds. Furthermore, although the preferred catalyst concentration range lies betextiles, leathers,

pressures higher than the vaporpressure oi the e monomer/dispersing agent system. i

The time requireddor thepolymerizationsis i largely dependent on the conditionsused, and may vary from a iew'hours to severaldays.

While the copolymers of this invention show far better heat and light stability than unmodified unsymmetrical dichloroethylene polymers, they do undergo some decomposition on long exposureto heat or light. The heat stability may be greatly improved by the addition of stabilizing agents such as epichlorohydrin, 1-pherioxy-2,3-

epoxypropane, 1-p-tolyl-2,3-epoxypropane, a, dimethylglycide, ethylglycidate, cadmium, copper, lead, and manganese salts of oleic, linoleic, stearic,

ricinoleic, palmitlc. lauric, and fatty oil acids in general, 4-cyclohexylmorplioline, glycine, leucine,

alanine, the N-octyl ester oiC-dimethylglycine,

and monocarboxylic acid amides preferably of the secondary or N-monosubstituted type, having heavy hydrocarbon residues preferably iormoi long chains. Compounds eilective as light stabilizers include eugenol, alkyl and aryl esters of salicyclicacid, and guaiacol. l

The copolymers of thisinventionare 'useiul tor.

the preparation oi plastics, coatings, fibers, films, and adhesives. Films may besubiected to a ing operation to improve their of these purposes the copolymers may be combined with or prepared in the presence of plasticizers, stabilizers, fillers, Pigments, dyes, softeners, natural resins or other synthetic resins. For many purposes the emulsion producedin the polymerization process may be used directly for ing applications. Specific surfaces to which coatings and impregnated compositions containing these copolymers may be applied include wood,

brick, concrete, plaster, and thelike.

The above description and examples arein tendedto be illustrative only. Anymodification of or variation therefrom which conforms tothe spirit of the inventionis intended to be within the scope of the claims. What is claimed is: f

-1. A copolymer of asymmetrical ene with, a fpolymerizable ketone which has a single aliphatic unsaturated group and in which the carbonyl group is attached to a carbon atom in turn attached by an ethylenic a methylene (CH2) group, the other valence or the carbonyl group being satisfied byamonovalent hydrocarbon radical, said copolymer conincluded taining 40-95% of dichloroethylene. i

2. A copolymer of asymmetrical dichloroethylf I l I ene with a polymerizable ketone whichhas a singlealiphatic unsaturatdgroupand. inwhich the carbonyl group is attached to acarbon atom F in the may be prepared both by casting from solution and by hot=pressingand cold rolling or cold draw- H strength. For any coatmetals, cloth, paper, stone.

dichloroethyldouble bond to chloroethylene. j i v v v 3. .A copo ymer of asymmetrical dichloroethylenewith a polymerizableketone which has a singleialiphatic unsaturated group and in which in m attached by an ethylenic double bond to a methylene (CHa) group, the other valence of the carbonyl group being satisfied-by an alkyl radical, saidcopolymercontainin: 40-95% of dithe carbonyl group is attached to a carbon atom in turn attached by an ethylenic double bond to 1 a methylene. .(CHzL groumthe other valence of the carbonyl group-being satisfied by alower alkyl radical, said copolymer containing 40-95% dichloroethylene.

4. A copolymer-oi asymmetrical dichloroethylene with methyl 'vinyl ketonaaald copolymer containing 40-95% or dichloroethylene.

5. A copolymer of asymmetrical dichlcroethylene withmethyl vinyl ketone; said polymer containing 40-95% of asymmetrical dichloroethylene and being admixed with astabilizing agent.

; 6. A; copolymer of. asymmetrical dichloroethylenewith phenyl vinyl ketone, said copolymer containing i -95% of gichloroethylenm '7. A copolymer o'f'aaymmetrical dichloroethylone with methyl isopropenyl ketone, saiciycopolymer containing 40-95% of dichloroethylene.

I 8. A copolymer of asymmetrical dichloroethylene with an alkyl vinyl ketone, said copolymer containing 40-95% oi dichloroethylene.

HAROLD wnmmn ARNOLD. Y

omomr: LowR-mcr: ponouqn. 

